Hydroxyarylthio anhydrides and analogues and derivatives thereof

ABSTRACT

Novel compounds of the formula: WHEREIN E IS FROM ZERO TO ONE AND D IS FROM ZERO TO ABOUT SIX, PROVIDED THAT WHEN E IS ZERO, Y1 is hydrogen; and that when e is one, Y2 is hydrogen; Y, Y1 and Y2 are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano, and halogen; Z is selected from the group consisting of -NH-, -O-, -S- and -CH CH-; A is aryl of six to 18 carbon atoms; and R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, carbalkoxy, carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halogen. Said compounds have utility as polymer additives. Novel polyester derivatives of the hydroxyarylthio succinic anhydride and thioanhydride compounds and a process for preparing said polyesters.

United States Patent [72] Inventors Emil J. Geering Grand Island;

Norman W. Dachs, Buffalo, both oi NY. [2]] Appl. No. 749,952

[22] Filed Aug. 5,1968 [45] Patented Dec. 7, l97l I73] Amuignee l'lookn Chemical Corporation Nlagara Falls, N.Y.

[54] HYDROXYARYLTHIO ANHYDRIDES AND ANALOGUES AND DERIVATIVES THEREOF 14 Claims, No Drawings [S2] U.S. Cl 260/347.2, 260/326.3, 260/326.5, 260/332.2, 260/332.3, 260/590, 260/47, 260/51, 260/75 Dmuchovsky et al., .I. Am Chem. Soc. (1964) Vol. 86 p. 2874-7 Primary E.mminerAlex Maze] Assistant Examiner Bernard 1. Dentz Al!0rneysPeter F. Casella, Donald C. Studley, Richard P.

Mueller and W. J. Schramm ABSTRACT: Novel compounds of the formula:

wherein e is from zero to one and d is from zero to about six, provided that when e is zero, Y is hydrogen; and that when e is one, Y is hydrogen; Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, arallkyl, hydrogen, cyano, and halogen; Z is selected from the group consisting of -NH, O-, -S- and -CH CH; A is aryl of six to 18 carbon atoms; and R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, carbalkoxy, carbaryloxy, alltoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy and halogen. Said compounds have utility as polymer additives. Novel polyester derivatives of the hydr'oxyarylthio succinic anhydride and thioanhydride compounds and a process for preparing said polyesters.

HYDROXYARYLTHIO ANHYDRIDES AND ANALOGUES AND DERIVATIVES THEREOF This invention relates to novel hydroxyarylthio compounds and a process for preparing said compounds by the reaction of mercaptophenols with reactive unsaturated compounds.

The addition of mercaptans to olefins is well known. This reaction is described by E. Emmet Reid in Organic Chemistry of Bivalent Sulfur, Vol. I 1, Chemical Publishing Co., N.Y.C., [960, pp. 29-34. The reactive unsaturated starting compounds of the present invention enter into reactions with phenol. Phenyl esters are formed by acetylation of phenol with, for example, citraconic anhydride. Anhydrides such as maleic anhydride react with phenol to give maleintype products such as phenolmalein. As phenols are readily alkylated by olefins, mercaptophenol similarly could also be expected to become alkylated by olefins.

Mercaptophenol is not only a mercaptan, but it is also a phenol and, therefore, has both a reactive hydroxyl group and a reactive ring. One might expect the above alternate reactions to take precedent over the addition of the mercaptan group to an unsaturated bond. One could not predict that the compounds of this invention would be produced by the reaction of a mercaptophenol and a reactive olefin.

In accordance with the present invention, there are provided novel compounds of the formula:

wherein:

a. e is from zero to one and d is from zero to about six;

b. provided that:

I. when e is zero, Y is hydrogen; and

2. when e is one, Y is hydrogen;

c. Y, Y and Y are of zero to about 20 carbon atoms and are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano and halogen;

d. Z is selected from the group consisting ofNH-,

e. A is aryl of six to 18 carbon atoms; and

f. R is of zero to about 20 carbon atoms and is selected from the group consisting of alkyl, aryl, aralkaryl, aralkyl,

carbalkoxy, carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxy, and halogen.

Also, in accordance with the present invention, there is provided a process for the preparation of the hydroxyarylthio succinic anhydride, succinimide, cyclohexenedione, and succinic thioanhydride compounds and novel polyester derivatives of the hydroxyarylthio succinic anhydride and thioanhydride compounds.

The following are typical of those compounds included within the scope of the present invention:

lethyll -(4-hydroxyphenylthio)succinimide l-cyano- I 2-hydroxyphenylthio )succinimide 2-( 3-hydroxyphenylthio)-5-cyclohexenl ,4-dione l-phenyl-2-( 2,3-dichloro-4-hydroxyphenylthio )succinic thioanhydride (Z-hydroxyphenylthio )succinic thioanhydride (2-hydroxyphenylthio)succinic anhydride (2-hydroxyphenylthiomethylene)succinic anhydride (4-hydroxyphenylthiomethylene)succinimide 5-chloro-6-(4-hydroxyphenylthio)-2-cyclohexenl ,4-dione l-propyl-2-(2-hydroxyphenylthio)succinic anhydride l-dodecyl-2-( 2-hydroxyphenylthio)succinic anhydride 2-( 2-hydroxy-4,5,6-trimethylphenylthio)-5-cyclohexenl ,4- dione l-benzyl-2-( 3-hydroxyphenylthio)succinic thioanhdride l-tolyl-2-( 4-hydroxyphenylthio )succinimide 2-( 3-hydroxyphenylthiomethylene succinic thioanhydride In the compounds of the present invention the carbonyl groups are activating groups that promote the addition reaction of a mercaptophenol to an unsaturated carbon--carbon bond.

R is preferably alkyl, aryl, hydroxy, or halogen. Y, Y and Y are preferably hydrogen or alkyl. R, Y, Y and Y are preferably of zero to about ten carbon atoms.

A is preferably phenyl, and in said] case, d is from zero to four.

When R, Y, Y or Y are halo, they may be chlorine, fluorine, bromine or iodine.

The unsaturated compounds that may be used as starting materials in the preparation of the compounds of the present invention are of the following formula:

wherein subscript e and Z, Y, Y and Y areas hereinbefore described. As indicated by the broken line, the unsaturation is at bond 1 and 2 when e is equal to zero and at bond 2 and 3 when e is equal to one. These compositions include compounds such as benzoquinone, maleic anhydride, itaconic anhydride, malimide and maleic thioanhydride.

The starting mercaptophenol compounds of the present invention are of the formula: HSA(R),,OH: wherein A, R and d are as hereinbefore described. Said compounds may be prepared by methods known in the prior art or by the procedure described in copending application Ser. No. 597,228, filed Nov. 28, 1966, now abandoned and refiled as S.N. 666,915, filed Sept. ll, 1967, now U.S. Pat. No. 3,468,961. Mercaptophenols, such as o-mercaptophenol, pmercaptophenol, 3,5-dimethyI-Z-mercaptophenol, 4-phenyl- 2-mercaptophenol, 3-cyano-2-mercaptophenol and 4-carboxy-3-mercaptophenol, are typical starting compounds.

The following reaction illustrates the process for the preparation of the novel compounds of the present invention.

Subscripts d and e, and Z, A, R, Y, Y and Y are as hereinbefore described.

Although the reaction may be conducted in the absence of a solvent, it is normally conducted in the: presence of a solvent. Typical solvents include benzene, toluene, xylene, heptane, hexane, chloroform, carbon tetrachloride, chlorobenzene, dioxane, N,N-dimethylformamide, N-methyl-Z-pyrrolidone, tetrahydrofuran and dimethylsulfoxide.

Although the reaction may be conducted at a temperature of about 0 to about 200 C., the preferred temperature is from about l0 to about C.

Although the reaction may be conducted in the absence of a catalyst, the time and temperature required to complete the reaction may generally be reduced by using a basic catalyst. A catalytic amount to about .05 mole of catalyst per mole of mercaptophenol is preferably employed. Suitable catalysts include salts of strong bases and alcohols or weak acids, amines, quarternary amine bases and alkali or alkaline earth metals or hydroxides. Examples of catalysts are sodium methylate, sodium acetate, potassium carbonate, triethyl amine, piperidine, triethylene diamine, trimethylbenzylammonium hydroxide and sodium or magnesium metal and sodium hydroxide.

The hydroxyarylthio succinic anhydrides and thioanhydrides of the present invention can be reacted with glycols or thioglycols to give the novel polyesters of the present invention.

Said novel polyesters contain at least one unit of the formula Y, Y, Y, A, R and subscripts d and e are as hereinbefore described.

The preferred polyesters of the present invention are of the formula R is alkylene ofone to aboutfive carbon atoms; R is alkylene of one to about five carbon atoms or phenylene, and W is oxygen or sulfur. Subscript a is from one to about 100; B is zero or one; c is from zero to about lO;fis zero or one; g is zero or one, provided that when 3 is one, c is greater than zero.

The even more preferred polyester compositions of the present invention contain at least one unit of the formula R and subscript d are as hereinbefore described.

Typical glycols or thioglycols that may be used as starting compounds in the preparation of the polyesters of the present invention are as follows: diethylene glycol, ethylene glycol, a, w-dihydroxy [poly(ethyleneoxides)], l,2-propylene glycol, 3,4-pentanediol, l,lO-decanediol, neopentyldiol, l,4- cyclohexanediol, diethanol sulfide, l,4-diethanolbenzene, 1,4- xylylenol, l,4,S,6,7,7-hexachloro-2,3-bis (hydroxymethyl)bicyclo-(2.2. l )-heptene-5,ethylenedithiol, hexamethylenedithiol, a, w-dimercapto(poly(ethylene sulfide)), l ,4-bis( mercaptomethyl)-cyclohexane l, l 2-dodecanedithiol and bis(mercaptoethyl)sulfide. Also, glycols and dithiols prepared by the oxyalkylation or thioalkylation of the above compounds and compounds such as 4,4'-isopropylidene diphenol, resorcinol, thiobisphenol, 4,4-dihydroxydiphenyl, aniline and methylamine.

In the process for the preparation of the novel hydroxyarylthio polyesters of the present invention, the glycol or thioglycol is reacted with the hydroxyarylthio succinic anhydride, or the corresponding dialkyl succinate, when a transesterification procedure is used, at a temperature of about 75 to about 250 C., for a period of about 3 to about 50 hours. No catalyst is required when the polyesterification is conducted by reaction of the hydroxyarylthiosuccinic anhydride. When a transesterification procedure is used useful catalysts are paratoluenesulfonic acid, or weakly acidic or basic catalysts such as calcium acetate or antimony trioxide.

Standard polyesterification procedures are applicable. For example, the rate of esterification can be increased by hastening the elimination of the condensation products, water or alcohol. Typically this is accomplished by passing an inert gas stream through the reaction mixture or by maintaining the mixture under reduced pressure. Water can also be removed as it forms by conducting the esterification in a water-imiscible solvent, such as toluene, whereby the water is distilled off as a component of an azeotropic distillate. The reaction is followed by periodically determining the carboxylic acid concentration or by monitoring the water or alcohol produced during the course of the reaction.

The carboxylic reagent need not be a single compound, but can be composed of several carboxylic compounds, of which one, several, or all can be hydroxyarylthio-substituted. Also the second reactant can be a mixture of several glycols or dimercaptans. Typical non-phenolic carboxylic reagents are fumaric acid, maleic anhydride, phthalic anhydride, pyromellitic anhydride, diethyl fumarate, dimethyl terephthalate, dimethyl l ,4,5,6,7,7-hexachlorobicyclo-(2.2. l )-5-heptane- 2,3-dicarboxylate.

A portion of the glycol or thioglycol can be replaced by trior higher substituted polyols or polythiols to give a crosslinked polymer. Typical polyols are l,l,l-trimethylopropane, glycerol, pentaerythritol, and oxyalkylated derivatives derived from sorbitol, sucrose and phenylenediamine.

A portion of the carboxylic reagent can be replaced with unsaturated anhydride or ester, such as those mentioned above, for example, maleic anhydride. The resulting polyester can be cross-linked via these unsaturated bonds with a vinyl monomer such as styrene.

The phenolic polyester compositions of this invention can be converted to epoxy derivatives by reaction with, for example, epichlorohydrin.

The phenolic polyester compositions of this invention can be converted to epoxy derivatives by reaction with, for example, epichlorohydrin.

The phenolic polyester compositions of this invention can be converted to a polyester substituted with aliphatic hydroxyl groups by treatment with an alkylene oxide, (oxyalkylation), such as ethylene oxide or propylene oxide. These ester polyols are useful as reagents for preparing polyurethane polymers by reaction with diisocyanates or polyisocyanates. Typical isocyanates are toluene diisocyanates and the phosgenated reaction products of formaldehyde and aniline.

The hydroxyarylthiosuccinic anhydrides, succinimides and succinicthioanhydrides of the present invention are useful when incorporated chemically into condensation polymers as stabilizers or as providers of hydroxy groups. The hydroxyl groups are used to chemically attach polymer modifiers, such as dyes, antistatic agents, hydrophobic or hydrophilic groups, and the like.

The polyesters of the present invention contain a reactive phenolic ring and hydroxy group and is therefore curable. Curing agents are carbonyl compounds, resoles, hexamethylenetetramine, polyisocyanates, diacid chlorides, diesters and the like. Reaction of the anhydride compositions of the present invention with carbonyl compounds, e.g., formaldehyde or acetone, under acid conditions with or without additional phenol present, gives carboxylic substituted bisphenol or novolak materials which may be esterified with long-chain alcohols to give reagents useful for imparting chemically bound plasticization to polymers, or which may be incorporated into polycarbonates, for example, to serve as crosslinking sites. Furthermore, reaction of the compounds of the present invention with carbonyl compounds under alkaline conditions gives methylol or resole-type materials that will cure on heating.

The following examples will further illustrate specific embodiments of this invention. It should be understood however that these examples are given by way of illustration and not limitation. All temperatures are in degrees centigrade and all parts are by weight, unless otherwise indicated.

To a stirred solution of 980 parts of maleic anhydride (10.1 moles), one part of triethylenediamine and 5600 parts toluene, was added 1260 parts of o-mercaptophenol (10.0 moles) over about a 15 minute period. The reaction was exothermic. After about one-half hour the reaction mixture was cooled to C. From a resulting thick slurry, 1900 parts of product were obtained on filtration. Concentration of the filtrate and further filtration resulted in more product. The combined product was recrystallized from toluene in fractions. The first crop, about 2040 parts, represented a 91 percent yield and melted in the range of 125-l 30 C. The total weight of all crystallization fractions corresponded to a yield of 98.5 percent. The product was identified as l-(2-hydroxyphenylthio )succinic anhydride.

Analysis Calculated for C l-LS: phenolic hydroxyl. 4.47%

acid and anhydride, 8.90% anhydride, 8.90% phenolic hydroxyl. 4.40% acid and anhydride, 8.80% anhydride. 8.74%.

EXAMPLE 2 Found Calculated l'or C H O S: C, 61.52% H, 4.30%

5. 13.69% OH, 7.24% C. 61.43% H. 4.34% S, 13.4% OH, 7.38%

Found EXAMPLE 3 in a manner similar to example 1, 2,4-di-t-butyl-6-mercaptophenol was reacted with maleic anhydride. The product, having a melting point of l37-139 C., was identified as l-(2- hydroxy-3,S-di-t-butylphenylthio)succinic anhydride.

Analysis Calculated for C,,,H,,O.S: C, 53.56% H, 3.60%

S, 14.30% OH, 7.57% C. 53.55% H, 3.44%

S, 14.2% OH, 7.45%

Found EXAMPLE 4 Analysis Calculated for C ,,H,,,O;NS:

Found S, 14.3% OH. 4.48% S, 14.02% OH, 4.4%

In a similar manner and in separate experiments, ethylmaleic thioanhydride and l-ethyl-2-methylenemaleic anhydride are reacted with 3,5-dimethyI-Z-mercaptophenol to yield the following respective products: 1-ethyl-2-(2-hydroxy-4,6- dimethylphenylthio)succinic thioanhydride and l-ethyl-2-(2- hydroxy-4,6-dimethylphenylthiomethylene)succinic anhydride.

EXAMPLE 5 To 58.3 parts of diethylene glycol were added 112 parts (0.5 moles) of (Z-hydroxyphenylthio)succinic anhydride. The mixture was warmed to a temperature of 85 C. at which temperature the anhydride went into solution. The solution was heated to 180 C. for 75 minutes during which period 514 parts of water were distilled off. The system was put under 175 millimeters of reduced pressure and the heating continued for 5 1 hour at 190 C. and for 3 hours at 170 C. The resulting product was a golden yellow resin.

Analysis-Acid value 0.07 mg. per 5; Calculated phenolic hydroxyl value 3.19 mg. per g. Found 3.20 mg. per g.

EXAMPLE 6 A low-molecular weight resole was prepared by a phenol, formaldehyde and sodium hydroxide condensation reaction. Equal amounts of said resole and the polyester of example 5 were stored at 85 to 95 C. for 3 days. The product was a golden yellow hard resin. When the resole is subjected to the same conditions, it becomes a deep red resin.

EXAMPLE 7' A stirred mixture of 1 12 parts (0.5 mole) of 2-hydroxyphenylthio)succinic anhydride and 33.2 parts (0.55 mole) of ethylene glycol were heated to 180 C. The mixture was held at 180 C. for a period of4 hours and during which time a gentle sweep of nitrogen is passed through the mixture. During the last 2 hours of said 4-hour period, the system was kept under a reduced pressure of 60 mm. The product was a pale yellow, clear resin.

Analysis Calculated hydroxy value 3.75 millliequivalents per g. Foundhydroxy 3.81 millicquivalents per g.

Molecular weight 847 While there have been described various embodiments of the present invention, the methods and compositions described are not intended to be understood as limiting the scope of the invention as it is realized that changes therein are possible.

What is claimed is:

11. A compound of the formula O Y L Y l 0 C -(OY2)e-S-A(R)d ll 12 0H wherein:

a. e is from zero to one and d is from zero to four;

b. provided that;

1. when e is zero, Y is hydrogen; and 2. when e is one, Y is hydrogen; c.Y, Y and Y are independently selected from the group consisting of hydrogen, chlorine, and a hydrocarbyl group of up to 10 carbon atoms selected from the group consisting of alkyl, phenalkyl and alkphenyl d. A is naphthyl or phenyl; and e. R is independently selected from the group consisting of chlorine, hydroxy, alkoxy of up to 10 carbon atoms of a hydrocarbyl group of up to 10 carbon atoms independently selected from the group consisting of alkyl, phenyl, and naphthyl; provided that phenyl and naphthyl be only a monosubstituent of A. 2. A compound according to claim 1, wherein R is selected from the group consisting of alkyl, phenyl, hydroxyl and chlorine.

3. A compound according to claim 2, wherein A is phenyl. 4. A compound according to claim 3,. wherein Y, Y and Y are selected from the group consisting of hydrogen and alkyl.

comprising reacting an equimolar amount of a compound of the formula 9 (1( t C Y O with a compound of the formula at a temperature of from about 0 C. to about 200 C. in the presence of a basic catalyst; wherein:

a. e is from zero to one and d is from zero to four;

b. provided that;

1. when e is zero, Y is hydrogen; and 2. when e is one, Y is hydrogen;

c. Y, Y and Y are independently selected from the group consisting of hydrogen, chlorine, and a hydrocarbyl group of up to 10 carbon atoms selected from the group consisting of alkyl, phenalkyl and alkphenyl;

d. A is phenyl or naphthyl; and

e. R is independently selected from the group consisting of chlorine, hydroxy, alkoxy of up to 10 carbon atoms and a hydrocarbyl group of up to 10 carbon atoms selected from the group consisting of alkyl, phenyl, and naphthyl; provided that phenyl and naphthyl be only a monosubstituent of A.

l l. The process of claim 10 wherein the mercapto phenol is of the formula (rod triethylenediamine.

Po-1050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 1, 5,97 l .Dated; December 7,: 1911 inventor) Emi l J. Geeri ng and Norman w, Dachs It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[- Abstract, line 9 "-CH CH-" should read -CH- '=CH- Column l line 7 'thioanhdride" should read ---th1'oanhydr1'de Column 3, line 56, "hexane l,l2" should read hexane, Column 6, l ine 2, "51 parts should read 6 parts line 65, "of a hydrocarbyl" should read and a hydrocarbyl --Q Column 7, line 30, the formula should be 0 (H II I C C Y 0 E c c (CY Column 8, line 28, the formula should read OH (lo -t l Signed and sealed this 6th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JRB 4 ROBERT GO'ITSCHALK fitesting Officer Commissioner of Patents J 

2. when e is one, Y2 is hydrogen; c. Y, Y1 and Y2 are independently selected from the group consisting of hydrogen, chlorine, and a hydrocarbyl group of up to 10 carbon atoms selected from the group consisting of alkyl, phenalkyl and alkphenyl d. A is naphthyl or phenyl; and e. R is independently selected from the group consisting of chlorine, hydroxy, alkoxy of up to 10 carbon atoms of a hydrocarbyl group of up to 10 carbon atoms independently selected from the group consisting of alkyl, phenyl, and naphthyl; provided that phenyl and naphthyl be only a monosubstituent of A.
 2. A compound according to claim 1, wherein R is selected from the group consisting of alkyl, phenyl, hydroxyl and chlorine.
 2. when e is one, Y2 is hydrogen; c. Y, Y1 and Y2 are independently selected from the group consisting of hydrogen, chlorine, and a hydrocarbyl group of up to 10 carbon atoms selected from the group consisting of alkyl, phenalkyl and alkphenyl; d. A is phenyl or naphthyl; and e. R is independently selected from the group consisting of chlorine, hydroxy, alkoxy of up to 10 carbon atoms and a hydrocarbyl group of up to 10 carbon atoms selected from the group consisting of alkyl, phenyl, and naphthyl; provided that phenyl and naphthyl be only a monosubstituent of A.
 3. A compound according to claim 2, wherein A is phenyl.
 4. A compound according to claim 3, wherein Y, Y1 and Y2 are selected from the group consisting of hydrogen and alkyl.
 5. A compound according to claim 1, wherein Y, Y1 and Y2 are hydrogen and d is zero.
 6. A compound of the formula
 7. The compound of claim 6 wherein d is two.
 8. The compound of claim 7 wherein R is t-butyl.
 9. The compound of claim 6 wherein d is zero.
 10. A process for preparing a compound of the formula
 11. The process of claim 10 wherein the mercapto phenol is of the formula
 12. A process in accordance with claim 10, wherein the reaction is conducted in the presence of a solvent.
 13. The process of claim 10 wherein the basic catalyst is an amine.
 14. The process of claim 10 wherein the catalyst is triethylenediamine. 